CN117165103A - Modification method of waste tire thermal cracking carbon black and carbon black obtained by modification method - Google Patents
Modification method of waste tire thermal cracking carbon black and carbon black obtained by modification method Download PDFInfo
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- CN117165103A CN117165103A CN202210574674.7A CN202210574674A CN117165103A CN 117165103 A CN117165103 A CN 117165103A CN 202210574674 A CN202210574674 A CN 202210574674A CN 117165103 A CN117165103 A CN 117165103A
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- 239000006229 carbon black Substances 0.000 title claims abstract description 261
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 193
- 239000010920 waste tyre Substances 0.000 title claims abstract description 48
- 238000002715 modification method Methods 0.000 title claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 104
- 239000002253 acid Substances 0.000 claims abstract description 85
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 32
- 229910000077 silane Inorganic materials 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 58
- 239000005060 rubber Substances 0.000 abstract description 58
- 230000003014 reinforcing effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000009472 formulation Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 239000004636 vulcanized rubber Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 19
- 238000011056 performance test Methods 0.000 description 18
- 238000005303 weighing Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- -1 silane compound Chemical class 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000565357 Fraxinus nigra Species 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006234 thermal black Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a modification method of waste tire thermal cracking carbon black and the carbon black obtained by the modification method. The method comprises the following steps: (1) subjecting the thermally cracked carbon black to a high temperature treatment; (2) Adding the thermal cracking carbon black subjected to the high-temperature treatment in the step (1) into an acid solution, stirring to obtain an aqueous suspension of the acid-washing thermal cracking carbon black, washing with water, and drying to obtain the acid-washing thermal cracking carbon black; (3) And (3) mixing the acid-washing thermal cracking carbon black obtained in the step (2) with a silane coupling agent for heat treatment to obtain the modified thermal cracking carbon black. The modification method reduces the ash content of the thermal cracking carbon black, enhances the surface activity of the thermal cracking carbon black, improves the reinforcing performance of the thermal cracking carbon black in rubber, and improves the use amount of the thermal cracking carbon black, so that the thermal cracking carbon black has wider application.
Description
Technical Field
The application relates to the technical field of modification of waste tire thermal cracking carbon black, in particular to a modification method of waste tire thermal cracking carbon black and carbon black obtained by the modification method.
Background
With the development of social economy in China, automobiles are increasingly integrated into production and life, the use amount of tires is also increased, and the serious problems of waste tire treatment and recycling are caused. The traditional methods such as direct burial, old tire retreading, rubber powder preparation and the like have the problems such as environmental pollution, narrow application range, resource waste and the like, and the thermal cracking treatment method of the waste tires is regarded as an environment-friendly and efficient treatment mode, so that the waste tires are treated, and meanwhile, the process of 'eating, drying and squeezing out' is truly realized, and the additional products with higher utilization value are obtained, so that the method has very important significance. The thermal cracking carbon black is used as an important product in the process of thermal cracking tires, and has the problem of poor reinforcing performance for a long time, so that the development of the whole thermal cracking industry is restricted.
Thermal cracking is to convert waste polymers (or biomass) into small molecular compounds and solid products at a proper temperature in an oxygen-free or inert atmosphere. The foreign study of thermal cracking was earlier, and Kaminsky et al, the university of German hamburger in the 70 s of the last century, began the study of thermal cracking of waste polymers. In contrast, with respect to thermal black, bouiereR J.M. in France in the last 80 th century found that thermal black contained higher ash content and residual pyrolysis oil, and the reinforcing property in rubber was poor. At present, thermal cracking carbon black directly obtained by thermal cracking of waste tires generally needs modification treatment to recover the reinforcing performance of the thermal cracking carbon black, so that the thermal cracking carbon black is applied to tires, and the additional value application range of products is further improved. However, the reinforcing performance of the modified carbon black in rubber is improved to some extent by ultrafine modification for the purpose of reducing the particle size or modification by a simple modifier, but the improvement range is limited, the level of high-performance carbon black or national standard requirements is difficult to reach, and a large amount of commercial carbon black can be mixed for ensuring the product performance, so that the use amount of thermal cracking carbon black is limited; the conventional acid washing modification efficiency is low, the surface activity of the thermal cracking carbon black can be greatly increased by strong acid, agglomeration is easier to form among carbon black particles, and the dispersibility of the carbon black in rubber is reduced, so that the performance of the carbon black rubber composite material is restricted.
Thus, there is an urgent need for a modification process that can simultaneously effectively reduce thermally cracked carbon black ash and avoid agglomeration problems.
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a modification method of waste tire thermal cracking carbon black and the carbon black obtained by the modification method. The modification method of the application comprises the following steps: firstly, pretreating a sample by high temperature under nitrogen atmosphere or vacuum, then carrying out acid washing to reduce ash content, and finally adding a coupling agent for grafting modification. The modification method improves the reinforcing performance of the thermal cracking carbon black in rubber, improves the use amount of the thermal cracking carbon black, and ensures that the thermal cracking carbon black has wider application.
The application aims at providing a modification method of waste tire thermal cracking carbon black.
The method comprises the following steps:
(1) Carrying out high-temperature treatment on the thermal cracking carbon black;
(2) Adding the thermal cracking carbon black subjected to the high-temperature treatment in the step (1) into an acid solution, stirring to obtain an aqueous suspension of the acid-washing thermal cracking carbon black, washing with water, and drying to obtain the acid-washing thermal cracking carbon black;
(3) And (3) mixing the acid-washing thermal cracking carbon black obtained in the step (2) with a silane coupling agent for heat treatment to obtain the modified thermal cracking carbon black.
In a preferred embodiment of the present application,
in the step (1), the step of (a),
the high temperature treatment is performed under nitrogen atmosphere or vacuum condition.
In a preferred embodiment of the present application,
in the step (1), the step of (a),
the high temperature treatment temperature is 300-600 ℃, preferably 400-500 ℃, more preferably 450-500 ℃, and the high temperature treatment time is 15 min-1 h, preferably 30 min-40 min.
In a preferred embodiment of the present application,
in the step (2), the step of (C),
the acid solution is one of nitric acid solution, hydrochloric acid solution and sulfuric acid solution;
the concentration of the acid solution is 2mol/L to 7mol/L, preferably 3mol/L to 5mol/L.
In a preferred embodiment of the present application,
in the step (2), the step of (C),
the mass ratio of the thermal cracking carbon black after the high-temperature treatment to the acid solution is 1:5-1:20, preferably 1:8-1:19.5.
In a preferred embodiment of the present application,
in the step (2), the step of (C),
stirring at 50-80 deg.c for 30 min-2 hr;
washing with water to pH 5-6, and drying.
In a preferred embodiment of the present application,
in the step (3), the step of (c),
the silane coupling agent is a polyether segment-containing silane polymer, (a polyether segment-containing silane polymer of patent application 202111383364.9 is employed and incorporated herein in its entirety)
The polyether segment-containing silane polymer has the general formula:
R x Si y O z (OR 1 ) w O(R 2 ) m Q n … … (I)
In the formula (I), x is 2 to 12, preferably 2 to 6;
y is 2 to 12, preferably 2 to 6;
z is 2 to 12, preferably 2 to 6;
w is 2 to 24, preferably 2 to 12;
m is 1-6;
n is 1 to 24, preferably 1 to 12;
r is C3-C36 straight-chain or branched or cycloalkyl or aralkyl or olefine, preferably C3-C18 straight-chain or branched alkyl;
R 1 methyl or ethyl;
R 2 is a fatty chain containing polyether structure, and has a structural formula of R 3 -(C 2 H 4 O) k -, where R is 3 Saturated fatty chain of C3-C18, k is an integer of 3-9;
q is S or SH.
The silane polymer is obtained by reacting a component comprising a silane compound and a fatty alcohol-polyoxyethylene ether, preferably the silane compound is selected from sulfur-containing silane containing methoxy and/or ethoxy, and the fatty alcohol-polyoxyethylene ether is selected from fatty alcohol-polyoxyethylene ether with a hydroxyl value of 95-180.
The preparation method of the silane polymer containing the polyether chain segment comprises the steps of heating and reacting components comprising silane compounds and fatty alcohol polyoxyethylene ether to obtain the silane polymer containing the polyether chain segment, and preferably, the preparation method specifically comprises the following steps:
step 1), adding the silane compound into a solvent for hydrolysis to obtain silane hydrolysate;
step 2), carrying out polycondensation reaction on the silane hydrolysate to obtain a silane polymer;
and 3) adding the fatty alcohol-polyoxyethylene ether into a silane polymer, and heating for reaction to obtain the silane polymer containing the polyether chain segment.
The silane polymer containing polyether chain segments is prepared from silane coupling agents containing methoxy or ethoxy which are commonly used in industry through polycondensation reaction between silanol, and then the silane polymer is obtained through reaction with fatty alcohol polyoxyethylene ether.
In the above preparation method, in the step 1):
the silane compound is selected from sulfur-containing silane containing methoxy and/or ethoxy, and can be specifically selected from at least one of Si69, si75, KH580, KH590 and other compounds;
the solvent is at least one selected from water and alcohol, preferably a mixed solvent of ethanol and water; the dosage ratio of the ethanol to the water in the solvent is 1:50-50:1, preferably 1:20-20:1;
the dosage ratio of the silane compound to the solvent is (1-100): 1, preferably (1 to 50): 1, more preferably (1 to 10): 1, a step of;
the hydrolysis temperature is 25-35 ℃ and the hydrolysis time is 1-5 hours;
the hydrolysis is also added with a pH regulator, wherein the pH regulator is at least one of hydrochloric acid, formic acid, acetic acid, sodium bicarbonate and sodium carbonate, and preferably at least one of hydrochloric acid, acetic acid and sodium bicarbonate; the pH regulator regulates the pH of the solution to 3-6.
In the above preparation method, in the step 2), the temperature of the polycondensation reaction is 0 to 100 ℃, preferably 25 to 60 ℃; the polycondensation reaction time is 1 to 10 hours, preferably 3 to 5 hours.
The preparation method comprises the following steps:
the fatty alcohol-polyoxyethylene ether is selected from fatty alcohol-polyoxyethylene ether with a hydroxyl value of 95-180;
the mol ratio of the fatty alcohol polyoxyethylene ether to the silane compound is (1-6): 1, preferably (1 to 3): 1, a step of;
the reaction temperature of the heating reaction is 100-150 ℃, preferably 110-130 ℃; the reaction time is 1 to 12 hours, preferably 1 to 6 hours;
a catalyst is also added in the heating reaction; wherein the catalyst is selected from titanate catalysts, preferably at least one of n-butyl titanate, tert-butyl titanate and isopropyl titanate; the dosage of the catalyst is 0.1-3% of the total dosage of the silane compound and the fatty alcohol-polyoxyethylene ether;
the heating reaction is carried out under the protection of inert gas; and vacuumizing treatment is also needed after the heating reaction, wherein the vacuumizing temperature is 50-80 ℃, and the vacuum degree in the reaction container is kept at minus 0.06-minus 0.1MPa.
In a preferred embodiment of the present application,
in the step (3), the step of (c),
the mass ratio of the acid-washing thermal cracking carbon black to the silane coupling agent is 8:1-15:1, preferably 10:1-13:1.
In a preferred embodiment of the present application,
in the step (3), the step of (c),
the mixed heat treatment of the acid-washing thermal cracking carbon black and the silane coupling agent is that the acid-washing thermal cracking carbon black and the silane coupling agent are mixed and then heat treated for 4 to 6 minutes at 140 to 160 ℃.
Typically, for ease of handling, it is preferred that the step (3) mixing process is performed in a high speed mixer; preferably, the heat treatment process in the step (3) is carried out in the rubber mixing process, namely, the heat treatment is carried out in an internal mixer for 4-6 minutes together with the rubber material at 140-160 ℃.
It is a second object of the present application to provide a carbon black prepared by the method of one of the objects of the present application.
The application adopts the following specific technical scheme:
the modification method of the thermal cracking carbon black of the junked tire comprises the following steps:
(1) The thermal-cracked carbon black is treated at high temperature to prepare for the subsequent steps.
(2) Acid washing and post-treatment are carried out on the thermal cracking carbon black obtained in the step (1): adding the thermal cracking carbon black subjected to high-temperature treatment into an acid solution according to a proportion, stirring at a high speed of 50-80 ℃ for 30 min-2 h to obtain a water suspension of the acid-washing thermal cracking carbon black, repeatedly washing with clear water until the pH value is 5-6, and drying to obtain the acid-washing thermal cracking carbon black.
(3) Mixing the acid-washing thermal-cracking carbon black obtained in the step (2) with a silane coupling agent in a high-speed stirrer according to a certain proportion, and performing heat treatment to obtain the modified thermal-cracking carbon black. The heat treatment of the acid-washed thermal cracking carbon black and the silane coupling agent is preferably carried out in the mixing process with rubber, and the specific steps are as follows: 1) Sequentially adding rubber, carbon black containing a silane coupling agent, zinc oxide and stearic acid into an internal mixer, and uniformly mixing at 50-60 ℃; 2) Heat-treating the sizing material in an internal mixer at 140-160 ℃ for 4-6 minutes, and discharging the sizing material; 3) And (3) after the sizing material is cooled to room temperature, placing the sizing material into an open mill, adding an accelerator and sulfur, and uniformly mixing.
The differences between the thermal cracking carbon black of the junked tires and the common carbon black are mainly focused on the following aspects: 1. morphology and particle size: the thermal cracking carbon black particles have blurred edges, irregular shapes, larger particle sizes and non-uniformity; BET specific surface area is small, and surface activity is poor; 3. the impurity content is too high, wherein the ash content is generally about 16-20%, and the components of the ash are ZnO and other metal oxides and SiO 2 Such non-metal oxides are the main.
Compared with the method of directly adopting acid washing, the method of adopting the method of firstly high-temperature pretreatment and then acid washing can reduce ash content more efficiently and improve acid washing efficiency; after that, the coupling agent provided by the application is adopted for modification, so that the mechanical property of the thermal cracking carbon black-rubber composite material can be effectively improved.
The beneficial effects of the application are as follows:
the modification method of the thermal cracking carbon black of the waste tires can improve the pickling efficiency, greatly reduce the ash content and improve the reinforcing performance of the thermal cracking carbon black in rubber.
Drawings
FIG. 1 is an electron micrograph of commercial carbon black N330;
FIG. 2 is an electron micrograph of unmodified thermally cracked carbon black;
FIG. 3 is an electron micrograph of thermally cracked carbon black after 30min of high temperature treatment at 500℃in a nitrogen atmosphere;
FIG. 4 is an electron micrograph of acid-washed thermal cracked carbon black of example 5;
FIG. 5 is an electron microscope image of thermal cracking of carbon black directly using 5mol/L hydrochloric acid to wash.
Detailed Description
The present application will be described in detail with reference to the following specific embodiments and the accompanying drawings, and it is necessary to point out that the following embodiments are merely for further explanation of the present application and should not be construed as limiting the scope of the present application, and some insubstantial modifications and adaptations of the application based on the present disclosure will remain within the scope of the application.
The starting materials used in the examples were all conventional commercially available.
TABLE 1 brands and sources of partial raw materials
| Name of the name | Suppliers (suppliers) |
| Thermal cracking carbon black | Commercially available |
| Carbon black N330 | Degusai |
| Carbon black N660 | Degusai |
| Sulfuric acid | Commercially available |
| Hydrochloric acid | Commercially available |
| Nitric acid | Commercially available |
The test instruments and test conditions used in the examples are as follows:
TABLE 2 test criteria/conditions
| Test item | Criteria/conditions |
| Carbon black ash content test | GB/T3780.10-2017 |
| Vulcanization performance test | GB/T9869 |
| Mechanical testing | GB/T528-2009 |
| Vulcanized rubber hardness test | GB/T6031-1998 |
Preparation of a silane coupling agent:
silane coupling agent 1:
10.86g (0.02 mol) of silane coupling agent Si69 is put into a mixed solvent with the ratio of ethanol to water being 20:1, wherein the dosage of the mixed solvent and the coupling agent Si69 is 1:5, formic acid is added to adjust the pH of the mixed solvent to 3, and hydrolysis is carried out for 1 hour under the condition of 25 ℃ to obtain hydrolysate containing silicon hydroxyl; then the silane coupling agent containing hydroxyl obtained by hydrolysis is stirred and polymerized for 5 hours at 25 ℃, then 11.64g (0.02 mol) of fatty alcohol polyoxyethylene ether-9 (hydroxyl value 95-100) and 0.675g of catalyst tetrabutyl titanate are added, the temperature is raised to 130 ℃ and nitrogen is introduced for protection, and the reaction is carried out for 2.5 hours. Finally, the temperature is reduced to 80 ℃, the vacuum degree of the system is kept at minus 0.08MPa, and the purification is carried out for two hours. The silane coupling agent 1 obtained is a compound containing the following general formula:
C 12 H 24 Si 4 O 2 (OC 2 H 5 ) 6 O[(C 2 H 4 O) 9 C 12 H 25 ] 2 S 8
silane coupling agent 2
10.86g (0.02 mol) of silane coupling agent Si69 is put into a mixed solvent with the ratio of ethanol to water being 20:1, wherein the dosage of the mixed solvent and the coupling agent Si69 is 1:4, acetic acid is added to adjust the pH of the mixed solvent to 3, and hydrolysis is carried out for 1 hour at 35 ℃ to obtain hydrolysate containing silicon hydroxyl; then the silane coupling agent containing hydroxyl obtained by hydrolysis is stirred and polymerized for 5 hours at 25 ℃, then 17.46g (0.03 mol) of fatty alcohol polyoxyethylene ether-9 (hydroxyl value 95-100) and 0.85g of catalyst tetrabutyl titanate are added, the temperature is raised to 130 ℃, and nitrogen is introduced for protection, and the reaction is carried out for 2.5 hours. Finally, the temperature is reduced to 80 ℃, the vacuum degree of the system is kept at-0.1 MPa, and the purification is carried out for two hours. The silane coupling agent 2 obtained is a compound containing the following general formula: c (C) 12 H 24 Si 4 O 2 (OC 2 H 5 ) 5 O[(C 2 H 4 O) 9 C 12 H 25 ] 3 S 8
Example 1
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 400 ℃ for 15min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into a 3mol/L hydrochloric acid solution according to the proportion of 10mL (10.5 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid-washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10:1 and the silane coupling agent 1 are mixed in a high-speed stirrer.
The heat treatment process of the acid-washing thermal cracking carbon black and the silane coupling agent 1 is carried out in the mixing process with rubber, and the specific operation steps are as follows: 1) Sequentially adding rubber, acid-washing thermal cracking carbon black mixed with a silane coupling agent 1, zinc oxide, stearic acid and uniformly mixing at 55 ℃ into an internal mixer; 2) Heat-treating the sizing material in an internal mixer at 150 ℃ for 5 minutes and discharging the sizing material; 3) After the sizing material is cooled to room temperature, placing the sizing material into an open mill, adding an accelerator and sulfur, and uniformly mixing; 4) Vulcanizing the mixed rubber at 145 ℃ to obtain vulcanized rubber; the formulation is shown in Table 3, and the results of the vulcanized rubber performance test are shown in Table 5.
TABLE 3 vulcanized rubber formulation
Example 2
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 15min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into a 3mol/L hydrochloric acid solution according to the proportion of 10mL (10.5 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid-washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 3
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into a 3mol/L hydrochloric acid solution according to the proportion of 10mL (10.5 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 4
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature for 1h after reaching 600 ℃, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into a 3mol/L hydrochloric acid solution according to the proportion of 10mL (10.5 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 5
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 6
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 8mL (8.6 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid-washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 7
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 15mL (16.2 g) of acid solution mixed with 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 8
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 50 ℃ for 30min, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid-washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 9
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 80 ℃ for 2 hours, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid-washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 10
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 2 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 2 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 11
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L sulfuric acid solution in a proportion of 10mL (13 g) of acid solution mixed with 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, drying the carbon black to obtain acid washing thermal cracking carbon black, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 12
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into a 5mol/L nitric acid solution according to the proportion of 10mL (13.5 g) of acid solution mixed with 1g of carbon black, stirring at a high speed for 1h at a temperature of 60 ℃, repeatedly washing the carbon black to pH=6 by using clear water, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Example 13
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; mixing the acid-washing thermal cracking carbon black with the silane coupling agent 1 according to the mass ratio of 13:1 for heat treatment.
The formulation and specific operation of the acid washing thermal cracking carbon black and silane coupling agent 1 mixed heat treatment process and modified thermal cracking carbon black used in rubber performance were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Comparative example 1
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; the thermal cracking carbon black after high temperature treatment is put into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirred for 1h at 60 ℃, repeatedly washed to pH=6 by using clear water, and the carbon black is dried to obtain the thermal cracking carbon black after acid washing.
The acid-washed thermal cracking carbon black was added to rubber according to the formulation of table 3, and the specific operation was as follows: 1) Sequentially adding rubber, carbon black, zinc oxide and stearic acid into an internal mixer, uniformly mixing at 55 ℃ and discharging rubber. 2) Placing the sizing material into an open mill, adding an accelerator and sulfur, uniformly mixing, and discharging slices to obtain the rubber compound. 3) And vulcanizing the mixed rubber at 145 ℃ to obtain vulcanized rubber. The results of the performance test of the vulcanized rubber of comparative example 1 are shown in Table 5.
Comparative example 2
Unmodified thermal black was prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the heat treatment process of mixing unmodified thermal cracking carbon black with silane coupling agent 1 and the performance of modified thermal cracking carbon black in rubber were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Comparative example 3
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature;
the thermally cracked carbon black treated at high temperature was added to rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the properties of the resulting rubber are shown in Table 5.
Comparative example 4
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; the thermally cracked carbon black treated at high temperature was prepared according to a ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The thermally cracked carbon black treated at high temperature was added to rubber according to the formulation of Table 3 and the specific procedure of example 1, and the properties of the resulting rubber are shown in Table 5.
Comparative example 5
Putting thermal cracking carbon black into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with each 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black after acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4;
the acid-washed thermal black was added to the rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the properties of the resulting rubber are shown in Table 5.
Comparative example 6
Putting thermal cracking carbon black into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with each 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black after acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; the thermally cracked carbon black after acid washing treatment is processed according to the following weight ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The acid-washed thermal black was added to the rubber according to the formulation of Table 3 and the specific procedure of example 1, and the properties of the resulting rubber are shown in Table 5.
Comparative example 7
And (3) turning the sequence of the step (1) and the step (2) to carry out experiments, wherein the steps are as follows:
putting thermal cracking carbon black into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with each 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, and drying the carbon black to obtain thermal cracking carbon black after acid washing; placing the acid-washed thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, cooling to the room temperature, and measuring ash content after modification treatment, wherein the ash content is shown in Table 4;
the modified thermal black was added to the rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the properties of the obtained rubber are shown in Table 5.
Comparative example 8
And (3) turning the sequence of the step (1) and the step (2) to carry out experiments, wherein the steps are as follows:
putting thermal cracking carbon black into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with each 1g of carbon black, stirring at a high speed for 1h at 60 ℃, repeatedly washing with clear water to pH=6, and drying the carbon black to obtain thermal cracking carbon black after acid washing; placing the acid-washed thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, cooling to the room temperature, and measuring ash content after modification treatment, wherein the ash content is shown in Table 4; the treated thermal cracking carbon black is prepared according to the following weight ratio of 10: and (1) mixing the mass ratio with the silane coupling agent 1 for heat treatment.
The formulation and specific operation of the modified thermal black and silane coupling agent 1 mixed heat treatment process and the performance of the modified thermal black in rubber were the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Comparative example 9
Weighing the waste tire thermal cracking carbon black, then placing the waste tire thermal cracking carbon black into a muffle furnace, heating the muffle furnace from normal temperature at a speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature at 500 ℃ for 30min, and then cooling to the room temperature; putting the thermal cracking carbon black subjected to high-temperature treatment into 5mol/L hydrochloric acid solution according to the proportion of 10mL (10.8 g) of acid solution mixed with 1g of carbon black, stirring at a high speed at 60 ℃ for 1h, repeatedly washing with clear water to pH=6, drying the carbon black to obtain thermal cracking carbon black subjected to acid washing, and measuring ash content after acid washing treatment, wherein the ash content is shown in Table 4; acid-washed thermal cracking carbon black is prepared according to the following ratio of 10:1, mixing Si69 in a mass ratio.
The formulation and specific operation of the modified thermal black and silane coupling agent Si69 mixed heat treatment process and the performance of the modified thermal black in rubber are the same as in example 1; the results of the vulcanized rubber performance test are shown in Table 5.
Comparative example 10
Unmodified thermally cracked carbon black ash was measured, see table 4; unmodified thermal black was added to the rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the resulting rubber properties are shown in Table 5.
Comparative example 11
Carbon black N330 was added to the rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the resulting rubber properties are shown in Table 5.
Comparative example 12
Carbon black N660 was added to the rubber according to the formulation of Table 3 and the specific procedure of comparative example 1, and the resulting rubber properties are shown in Table 5.
TABLE 4 carbon black ash
TABLE 5 rubber Properties
As can be seen from comparative examples 3 and 4, the rubber composite material is modified only by high temperature treatment or by adding a coupling agent after high temperature treatment, and the tensile strength is greatly reduced although the tensile strength of the rubber composite material is improved; as can be seen from comparative examples 5 and 6, the thermal cracking carbon black is modified directly by acid washing or by adding a coupling agent after acid washing, the ash content is reduced slightly, the acid washing efficiency is low, and the mechanical property of the rubber composite material is improved slightly; the difference of ash reduction effects obtained by applying the same pickling treatment conditions under different high-temperature treatment conditions in example 1, example 2 and example 3 is larger, which indicates that sufficient high-temperature treatment can improve the pickling effect; as can be seen from table 4, the ash content of the thermally cracked carbon black can be effectively reduced by performing a sufficient amount of acid solution treatment after the high temperature treatment; in comparative examples 7 and 8, the order of acid washing and high temperature was reversed, the reduction of ash was small, and the acid washing efficiency was low, demonstrating the importance of the experimental order in the present application; as can be seen from the data in Table 5, the method for treating the thermal-cracking carbon black of the waste tires, provided by the application, can effectively improve the stretching strength and hardness of the thermal-cracking carbon black-rubber composite material on the premise of keeping higher tensile strength, reach the level of a higher reference sample (namely, exceeding the level of N660 and approaching the level of N330), and improve the reinforcing performance of the thermal-cracking carbon black in the rubber material. Comparative example 9 the mechanical properties of the carbon black-rubber composite were lowered although the heat treatment and acid treatment steps were the same as in the present application, but the silane coupling agent of the final mixed heat treatment was not the silane coupling agent of the present application.
As can be seen from fig. 1 and 2, compared with commercial carbon black, the thermal cracking carbon black has large and uneven surface morphology particle size, blurred particle edges and different shapes, and is adhered to each other. As can be seen from fig. 3, the thermally cracked carbon black particles became clear at the edges after the high temperature heat treatment, and exhibited a spherical shape. As can be seen from fig. 4 and fig. 5, the pickling effect can be effectively improved by adopting high-temperature heat treatment under nitrogen atmosphere before pickling, the microstructure of the thermal cracking carbon black after pickling is closer to that of commercial carbon black, the impurity coverage is obviously reduced, the pores among aggregates are more, and the characteristics of nano particles are more obvious.
Claims (10)
1. A modification method of waste tire thermal cracking carbon black is characterized by comprising the following steps:
(1) Carrying out high-temperature treatment on the thermal cracking carbon black;
(2) Adding the thermal cracking carbon black subjected to the high-temperature treatment in the step (1) into an acid solution, stirring to obtain an aqueous suspension of the acid-washing thermal cracking carbon black, washing with water, and drying to obtain the acid-washing thermal cracking carbon black;
(3) And (3) mixing the acid-washing thermal cracking carbon black obtained in the step (2) with a silane coupling agent for heat treatment to obtain the modified thermal cracking carbon black.
2. The modification process of claim 1, wherein:
in the step (1), the step of (a),
the high temperature treatment is performed under nitrogen atmosphere or vacuum condition.
3. The modification process of claim 1, wherein:
in the step (1), the step of (a),
the high temperature treatment temperature is 300-600 ℃, preferably 400-500 ℃, and the high temperature treatment time is 15 min-1 h, preferably 30 min-40 min.
4. The modification process of claim 1, wherein:
in the step (2), the step of (C),
the acid solution is one of nitric acid solution, hydrochloric acid solution and sulfuric acid solution;
the concentration of the acid solution is 2mol/L to 7mol/L.
5. The modification process according to claim 4, wherein:
in the step (2), the step of (C),
the mass ratio of the thermal cracking carbon black after the high-temperature treatment to the acid solution is 1:5-1:20.
6. The modification process of claim 1, wherein:
in the step (2), the step of (C),
stirring at 50-80 deg.c for 30 min-2 hr;
washing with water to pH 5-6, and drying.
7. The modification process of claim 1, wherein:
in the step (3), the step of (c),
the silane coupling agent is a silane polymer containing polyether chain segments and has the following general formula:
R x Si y O z (OR 1 ) w O(R 2 ) m Q n … … (I)
In the formula (I), x is 2 to 12, preferably 2 to 6;
y is 2 to 12, preferably 2 to 6;
z is 2 to 12, preferably 2 to 6;
w is 2 to 24, preferably 2 to 12;
m is 1-6;
n is 1 to 24, preferably 1 to 12;
r is C3-C36 straight-chain or branched or cycloalkyl or aralkyl or olefine, preferably C3-C18 straight-chain or branched alkyl;
R 1 methyl or ethyl;
R 2 is a fatty chain containing polyether structure, and has a structural formula of R 3 -(C 2 H 4 O) k -, where R is 3 Saturated fatty chain of C3-C18, k is an integer of 3-9;
q is S or SH.
8. The modification process of claim 7, wherein:
in the step (3), the step of (c),
the preparation method of the silane polymer containing the polyether chain segment comprises the steps of heating and reacting components comprising silane compounds and fatty alcohol polyoxyethylene ether to obtain the silane polymer containing the polyether chain segment.
9. The modification process of claim 1, wherein:
in the step (3), the step of (c),
the mass ratio of the acid-washing thermal cracking carbon black to the silane coupling agent is 8:1-15:1, preferably 10:1-13:1;
the mixed heat treatment of the acid-washing thermal cracking carbon black and the silane coupling agent is that the acid-washing thermal cracking carbon black and the silane coupling agent are mixed and then heat treated for 4 to 6 minutes at 140 to 160 ℃.
10. A carbon black prepared by the method of any one of claims 1-9.
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